Method for antirust treatment of steel stocks

ABSTRACT

A steel stock such as hot-rolled pickled steel plate, cold-rolled steel plate, cast iron or the like is subjected to antirust treatment with an aqueous solution or an emulsion consisting mainly of a 1-hydroxybenzotriazole compound represented by the general formula: ##STR1## where X and Y represent hydrogen atoms and hydroxy, alkyl, carboxyl, nitro and sulfonic groups, and further containing one or more of aliphatic dicarboxylic acids added thereto, and having a pH within the range of 7-10.

TECHNICAL FIELD

The present invention relates to antirust treatment of steel stocks or materials such as hot-rolled pickled steel plate, cold-rolled steel plate, cast iron and so on.

BACKGROUND OF THE ART

Usually surface treatment is applied to the surface of cold-rolled steel plates, etc. for anticorrosion and preservation of fine appearance.

That is, because a considerable time passes before such various types of steel plates and so on are processed and used, they are coated with an antirust oil or chemically treated or are packed in vaporable antirust paper or are otherwise treated to prevent rust. Any of these prior art methods for anticorrosion, however, has the following drawbacks.

The application of antirust oil will incur, not to mention stickness of oil, the necessity for a degreasing step when the steel plates are in use, followed by the treatment of the exhausted degreasing solution, which is troublesome.

In addition, welding or like processing of materials with antirust oil applied thereto presents problems in that the electrodes become dirty, fuming becomes significant and the preservation of a good working circumstances is adversely affected.

Already publicly known water soluble antirust agents, for example, sodium nitrite, sodium borate, aromatic carboxylic acids, imidazoles, amines and surfactants are used alone or in combination. However, their antirust effect is useful mainly in water or in the air, and is rather poor when the steel plates contact one another in a wet atmosphere or under conditions where water is attached to them or when they are stacked at high temperature and high humidity, namely, in a wet box as specified by JIS Z-0228. Further, there are antirust agents with higher aliphatic amines or higher fatty acids incorporated therein. However, they also have drawbacks that their drying characteristics are bad and that a removal step is required as in the case of the use of antirust oil.

The inventors of the present invention have already discovered that 1-hydroxybenzotriazole has an excellent antirust effect for steel stocks as is described in Japanese patent publication No. 27694/78. However, it has been found that there is in this case a weakness that the discoloration or staining is produced in some cases if water is dropped on a treated steel plate, and another treated one is stacked thereon and allowed to stand at high temperature and high humidity atmosphere, although their antirust properties are very excellent after they are subjected to hot-air drying.

The present invention has overcome these drawbacks of the prior art methods and has further made it possible to exert an extremely good antirust effect without necessity for any further treatment in the subsequent steps.

DISCLOSURE OF THE INVENTION

In summary, the present invention is characterized by adjusting an aqueous solution of 1-hydroxybenzotriazole and an aliphatic dicarboxylic acid to within a neutral range with a neutralizing agent and applying the adjusted solution to the surface of metals to form an antirust coating.

The effects of the present invention are not limited to antirust ones in a particular environment. The antirust effects are excellent not only in water but also in the air, and in an acidic atmosphere or in an atmosphere of high temperature and high humidity where water droplets are present between the contacted treated steel plates or in other various environments where a temper rolling solution is scattered or its vapor attaches as water droplets on steel plates rolled in a high speed temper rolling step.

According to the present invention, a mixed aqueous solution consisting mainly of a 1-hydroxybenzotriazole compound represented by the general formula: ##STR2## Where X and Y represent hydrogen atoms and hydroxy, alkyl, carboxyl, nitro and sulfonic groups, and containing simultaneously an aliphatic dicarboxylic acid, for example, one or more of suberic acid, azelaic acid and brassylic acid, is neutralized with ammonia water, hydrazine or an alkanol amine such as monoethanol amine or triethanol amine to provide an aqueous solution having a pH within the range of 7-10 which is applied to steel stocks. The aqueous solution may be used after a water-soluble high molecular compound or a surfactant is added thereto. Further, the object may be attained by applying to the surface of steel stocks a solution obtained by adding the mixed aqueous solution to an emulsion such as an aqueous mixture of cutting oil, abrasive oil or rolling oil, whereby an antirust coating is formed. In this instance, the concentration of the 1-hydroxybenzotriazole of the above general formula and its derivatives contained in the resulting solution is within the range of 0.01-10% (% used herein is by weight), and the aliphatic dicarboxylic acid added thereto may be employed within the range of 0.01-5%. Particularly preferably, each of the 1-hydroxybenzotriazole, main component, and the aliphatic dicarboxylic acid, additive, is used in the range of 0.1-2% from the standpoint of the antirust and economic aspects. Further, a proportion of 0.001-0.5% for the surfactant if added and a proportion of 0.01-2% for the high molecular compound if added are preferred from viewpoints of antirust and uniformity of the resulting coating, which will contribute to the enhancement of the anticorrosive properties.

It is a characteristic feature of the present invention that direct painting or direct plating is possible to the surface of steel stocks treated according to the present invention, which exerts effects equivalent to those of cases where painting or plating is applied to the surface of metals not subjected to any treatment.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereunder, there are given examples of the present invention.

EXAMPLE 1

An aqueous solution containing 0.5% of 1-hydroxybenzotriazole and 0.3% of azelaic acid was adjusted to pH 8 by the addition of monoethanol amine as the neutralizing agent to give a treating solution. A steel material was subjected to the conventional temper rolling, and water was purposely applied to a part of the steel material at the exit, which was coiled as it was.

EXAMPLE 2

An aqueous solution prepared by adding 0.2% azelaic acid and further 0.03% of a nonionic surfactant (a polyoxyethylene alkyl ether) to 0.4% of 1-hydroxybenzotriazole is adjusted to pH 8 by the addition of monoethanol amine as the neutralizing agent to give a treating solution. This treating solution is sprayed continuously over a surface-cleaned cold-rolled steel plate. Immediately thereafter, the plate is treated with rubber rolls and dried with a drier.

EXAMPLE 3

An aqueous solution prepared by adding 0.3% of sebacic acid and 0.1% of an acrylic resin, a water-soluble high molecular material, to 0.4% of 1-hydroxybenzotriazole is adjusted to pH 8 by the addition of triethanolamine as the neutralizing agent to prepare a treating solution. This treating solution is sprayed continuously over a surface-cleaned cold-rolled steel plate, and immediately the plate is treated by rubber rolls and dried with a drier.

The results of antirust tests using steel plates treated according to the above method of the present invention and controls are shown in Table 1, and the results of direct painting, in Table 2.

EXAMPLE 4

An aqueous solution, prepared by adding 0.2% of sebacic acid and 0.03% of a nonionic surfactant (a polyoxyethylene alkyl ether) to 0.5% of 1-hydroxybenzotriazole, is adjusted to pH 9.0 by the addition of monoethanolamine as the neutralizing agent to give a treating solution. It is sprayed continuously over a surface-cleaned cold-rolled steel plate. Immediately thereafter, the plate is treated with rubber rolls and dried with a drier.

                                      TABLE 1                                      __________________________________________________________________________     Results of antirust tests                                                               Housing test in wet box*                                                            Stacked                                                                             Stacked                                                                   after                                                                               after      In 0.6 N                                                       drop-                                                                               drop-      HCl                                                            ping of                                                                             ping of                                                                             Indoor                                                                               atmosphere                                                Stacking                                                                            treating                                                                            tap  exposure                                                                             for 24                                                    condi-                                                                              solution                                                                            water                                                                               for 10                                                                               hours                                                     tion (1)  (2)  days  (3)                                              __________________________________________________________________________     Present invention                                                              Example 1                                                                               Coiled                                                                              --   --   ⊚                                                                     ⊚                                          and al-                                                                        lowed to                                                                       stand in                                                                       plant for                                                                      1 month                                                               Example 2                                                                               ⊚                                                                    ⊚                                                                    ⊚                                                                    ⊚                                                                     ⊚                                 Example 3                                                                               ⊚                                                                    ⊚                                                                    ⊚                                                                    ⊚                                                                     ⊚                                 Example 4                                                                               ⊚                                                                    ⊚                                                                    ⊚                                                                    ⊚                                                                     ⊚                                 Controls**                                                                     Ammonium ○                                                                            ○                                                                            Δ                                                                             X     X                                                sebacate                                                                       Triethanol                                                                              ○                                                                            ○                                                                            Δ                                                                             X     X                                                amine                                                                          azelate                                                                        1-hydroxy-                                                                              ⊚                                                                    ⊚                                                                    Δ ˜ ○                                                            ○                                                                             ○                                         benzotriazole                                                                  ammonium                                                                       Commercially                                                                            ○                                                                            ○                                                                            Δ                                                                             X     X                                                available                                                                      product A                                                                      No treatment                                                                            XX   --   XXX  XX    XXX                                              __________________________________________________________________________      In the table,                                                                   *Ten test pieces of 10 × 10 cm subjected to a seven day housing         test in a wet box (50° C., 98% RH) were bound tightly by the use o      a miniature vise and then subjected to the tests.                              **The concentration of all the treating solutions used as the controls wa      1%, and the treatment using them was made by the same procedures as in th      case according to the present invention.                                       (1): The aqueous treating solution was dropped on the treated steel            plates, and the treated steel plates were stacked for the tests.               Discoloration and rust condition of the portions on which the solution wa      dropped were evaluated.                                                        (2): Tap water was dropped on the treated steel plates, and the treated        steel plates were stacked and tested. Rust condition of the portions on        which the water was dropped was evaluated.                                     (3): In the bottom of a desiccator, there was placed a 0.6 N aqueous HCl       solution, and the treated steel plates were placed on a perforated plate       in the desiccator by the capping. Rust condition after 24 hours was            evaluated.                                                                     (4): The commercially available product A was of sodium nitrite system.        Evaluations: ⊚ . . . No change; ○ . . . Slight           discoloration; Δ . . . Rust is noticeable; X . . . About 10% rust;       XX . . . About 30% rust; XXX . . . More than 60% rust.                   

                  TABLE 2                                                          ______________________________________                                         Direct painting properties                                                                    Primary Secondary                                                              adhesion                                                                               adhesion                                                               properties.sup.(1)                                                                     properties.sup.(2)                                      ______________________________________                                         Treated steel plates                                                                            10        10                                                  in Examples 1-3 of                                                             the present invention                                                          Material treated with                                                                            9         7                                                  commercially availa-                                                           ble product A                                                                  Untreated material                                                                              10        10                                                  ______________________________________                                          Paints used . . . Acrylic and epoxyurea paints                                 .sup.(1) Crosscut Ericksen 7 mm, unit 2 mm. The coating was peeled off by      the cellophane tape, and the evaluation was made on the basis of ease of       peeling.                                                                       .sup.(2) Adhesion properties of the coating were tested immediately after      the sample used in the primary adhesion test was immersed in deionized         water at 40° C. for 24 hrs.                                             The test items are the same as in the primary adhesion test.                   Evaluations: 10 (Excellent)-0 (Failure)                                  

AVAILABILITY IN INDUSTRY

Thus, according to the present invention, not only the intended antirust effects can be fully displayed in various surrounding conditions but also no work in removing the anticorrosive agent before the next step is necessary, and painting or other required treatments may be conducted directly, so the workability can be improved. Further, a problem of toxicity resulting from the treatment has recently arisen in the case of the conventional treatment involving the use of sodium nitrite, whereas in case of the present invention, such toxicity is extremely low, and in the welding or like operations, there is no environmental pollution caused by fuming, nor any lowering of workability caused by staining of the electrodes. Thus, the present invention has excellent advantages as compared with the conventional surface treatment methods. 

We claim:
 1. A method for antirust treatment of steel stock which comprises treating the steel stock with an aqueous solution or an emulsion containing 0.01-10% by weight of a 1-hydroxybenzotriazole compound represented by the general formula: ##STR3## where X and Y represent hydrogen atoms, hydroxy, alkyl, carboxyl, nitro or sulfonic groups, and further containing 0.01-5% by weight of one or more of C₈ -C₁₃ dialkanoic acids, and having a pH within the range of 7-10.
 2. The method according to claim 1 wherein said dialkanoic acid is suberic, azelaic, sebacic or brassylic acid.
 3. The method according to claim 2 wherein said dialkanoic acid is azelaic or sebacic acid. 